Double-ordered manganites LnBaMn2O6–δ (Ln = Nd, Sm) were shown to possess a variable oxygen content from δ = 0 to 1 while maintaining a tetragonal structure within the temperature range of 973–1223 K and under partial oxygen pressure 10−22 – 1 atm. Coulometric titration technique was successfully utilized to reveal three separated phase in these materials depending on oxygen content. Thermodynamic analysis based on experimentally obtained isothermal functions δ=f(pO2) enabled one to develop a defect formation model suggesting a coexistence three main processes of defect formation in the studied oxides. Thus oxidation and partial disproportionation of manganese supplemented by intrinsic oxygen disordering were demonstrated to govern defect equilibrium. Different influence of activity coefficients involved in the thermodynamic model was considered. Moreover, a reduction in the radius of lanthanide was found to be favorable to expand oxygen homogeneity region and to decrease in the enthalpy of oxidation reaction.